Production of waxlike substances



Patented Feb. 10, 1942 UNITED STAT 2,252,466 2 PRODUCTION or waxmmSUBSTANCES Hans Georg Hnmmel, Mannheim, and Michael Jahrstorier,Ludwigshaien-on-the-Rhine, Germany, assignors, by mesne assignments, toGeneral Aniline & Film Corporation, New York, N. Y., a corporation ofDelaware No Drawing. Application November 3, 1938, Se-

rial No. 1937 12 Claims.

The present invention relates to a process for producing wax-likesubstances by condensing polycarboxylic acids and amines. I

We have found that wax-like substances which are very valuableindustrially can be obtained by condensing aliphatic amines having atleast one high molecular alkyl radical i. e. a radical containing atleast 8 carbon atoms and at least one hydrogen atom attached to nitrogenwith cyclic polycarboxylic acids which are not capable of forming inner,anhydrides. acids there may be mentioned-particularly such as arederived from the benzene series for example isophthalic acid,terephthalic' acid, diphenyl-4.4 dicarboxylic acid, naphthalene-1.4-(l.5-, -l.6- and 2.64 dicarboxylic acids. Furthermore polycarboxylicacids, such as trimesic acid, trimesic acid the nucleus of which ispartially .or completely hydrogenated, symmetric benzene tribenzoicacid, diphenyl- 2.4.3-tricarboxylic acid andpyridine-1.3.5-tricarboxylic acid which can be obtained by oxidizingcollidine may be used. The said polycarboxylic acids may also containsubstituents, as for example halogen atoms or hydroxyl, ether, ester ornitro groups, such as chloror nitro-terephthalic acid. Instead of thecarboxylic acids, their functional derivatives, as for example theirchlorides or esters, may also be used.

Suitable amines for the process are for example octylamine, decylamine,dodecylamine, methyldodecylamine, N-cetylethvlenediamine, asymmetricN-dicetylethylene-diamine,

decylamine, cyclohexyldecylamine, beta-ethylhexylamine,N-methyl-cetyl-amine, N-propylricinolamine, and also amine mixtures suchas are obtained for example by reduction of amides or nitriles of thecarboxylic acid mixtures contained in fatty substances of vegetal originsuch as oils or iats or carboxylic acid mixtures obtained by oxidationof high molecularweight paraiiin hydrocarbons, or by the reaction .ofmineral acid esters of fatty alcohols with ammonia or primary amines.

Generally speaking the amines and polycarboxylic acids are used inequivalent amounts. Smaller or larger amounts of amine may, however, beused. In many cases it is preferable to replace a part of the amines byaliphatic polyamines, as for example ethylene diamine, diethylenetriamine or triethylene tetramine or mixtures of the same. It may alsobe advantageous to replace a part of the cyclic polycarboxylic acids bymonobasic or dibasic aliphatic As polycarboxylic 238,618. In GermanyNovember 22,

(Cl. 260404)' v vcarboxylic acids or mixtures thereof. Forexoctadecylamine or oleylamine, hyd'roxyethyldoample high-molecularfatty acids as are contained in fatty substances of vegetal origin suchas oils, fats or waxes, such as caproic acid, lauric acid, stearic acidor montanic acid may be employed or acids obtained by oxidizinghigh-molecular paraiiinic hydrocarbons may be employed. Suitabledicarboxylic acids are for example malonic acid, succinic acid, adipicacid or mixtures of dibasic acids as are obtained by oxidizinghigh-molecular paraffin hydrocarbons with nitric acid.

The condensation takes place generally speak- I ing even by simpleheating of the polycarboxylic acids with the amines to hightemperatures, as for example temperatures above C. It is advantageous towork at temperatures between and 300 C. The heating of the mixture ispreferably continued until water has distilled oil in an amountapproximately corresponding to the amount of water theoreticallycalculated for amide formation from the initial materials used.

The condensation may also be carried out in the presence of solvents ofhigh boiling point, as for example tetrahydronaphthalene,trichlorbenzene or nitrobenzene, or with an addition of oils, tats orwaxes of the acids contained therein. When using acid halides, it ispreferable to work in the presence of agents binding acids, as forexample caustic soda solution, caustic potash solution, ammonia or soda.

Depending on the nature of the initial materials used, wax-likesubstances of very high melting point are obtained which have valuableindustrial properties and which if desired may be subjected topurification, as for example by treatment with adsorbent or bleachingsub-.

are soluble inhigher boiling' organic solvents,

such as xylene, oil or turpentine, mineral oil fractions and also inoils, fats, paraflin waxes, ozokerite, ceresine, natural or syntheticwaves and similar products and may be used with advantage for manypurposes in industries working up waxes. For example they are suitablealone or together with other substances for impregnating textiles, paperand the like. The products also have a very high binding power for thesolvents usual in industries working up waxes. The good oil-bindingpower of the products oifers special advantages in the preparation andstorage of wax finished products, such as shoe creams and polishingcompositions.

The following examples will further illustrate how the present inventionmay be carried out in practice but the invention is not restricted tothese examples. The parts are by weight.

Example 1 100 parts of terephthalic acid and 325 parts of octadecylamineare heated until about 20 parts of water have distilled off, whereby thetemperature rises from 180 to 300 within about 3 hours.

A rather hard, almost colorless, wax-like prod- 160 parts ofterephthalic.acid dimethyl ester and 310 parts of dodecylamine areheated until about 50 parts of methyl alcohol have distilled oil". Theresidue is a hard, colorless wax-like product having a dropping point of166 and a softening point of 164 C.

Example 3 100 parts of terephthalic acid and 230 parts of dodecylamineare introduced into about 1700 parts of tetrahydronaphthalene, themixture then being heated to boiling under a reflux condenser providedwith a water separator until water no longer passes over. Afterdistilling off the tetrahydronaphthalene in vacuo, there remains a paleyellow, rather hard wax having a dropping point of 164 and a softeningpoint of 163 C. It is well soluble in fused paraffin wax, in natural andsynthetic ozokerite and in oils, as for example linseed oil.

Example 4 A mixture of 100 parts or terephthalic acid and 320 parts ofoleylamine are heated under a descending condenser. The splitting oil ofwater commences at 225 C. and is completed after about 3 hours when atemperature of 320 C. is reached. The condensation product is a yellowsoft wax having a dropping point of 124 and a softening point of 115 C.It is well soluble when hot in alcohols and aromatic hydrocarbons and infats V and waxes.

Isophthalic acid may be used instead of terephthalic acid; a dark yellowsoft wax having a dropping point of 91 C. is thus obtained.

Example 5 300 parts of diphenyl-414'-dicarboxylic acid and 700 parts ofoctadecylamine are heated for about an hour until the amount of watercalculated from the formation of the dicarboxylic acid diamide hasdistilled off. The residue solidifies when cooled to form a yellow, hardwax-like mass having a dropping point of 199 and a softening point of173 C.

. Example 6 270 parts of diphenyl-4.4-dicarboxy1ic acid dimethyl esterand 380. parts of dodecylamine are heated until methyl alcohol no longerdistils over. A dark yellow wax-like mass is obtained which has adropping point of 205 and a softening point of 195 C.

ylamine instead of the dodecylamine, a wax-like mass having a droppingpoint of 176 C. is obtained.

, Example 7 A mixture of parts of terephthalic acid, 178 parts ofdodecylamine and 10 parts of ethylene diamine hydrate is heated. Afterdistilling off 20 parts of water, there remains a pale yellow. hardwax-like mass having a dropping point of 251 and a softening point of180 C. The prodnot is well soluble in paraffin wax, waxes and similarsubstances.

Example 9 A mixture of 166 parts of terephthalic acid, 146 parts ofadipic acid and 740 parts of dodecylamine is heated for an hour at from200 to 300 C. After distilling off 70 parts of water, a hard, palebrown, wax-like mass is obtained having a dropping point of 153 and asoftening point or c. It is soluble in higher boiling organic solvents,such as xylene, and also in paraffin wax, ozokerite, oils, fats andwaxes.

Example 10 Example 11 1 molecular proportion of isophthalic acid isheated with 2 molecular proportions of dodecylamine at from about 200 to240 C. until about 2 molecular proportions of water have distilled off.

The condensation product is a hard yellow wax having a dropping point of124 and a softeninz point of 123 C.

By using octadecylamine instead of dodecylamine, a wax having a droppingpoint of 119 .and a softening point of 118 C. is obtained.

Example 12 A mixture of 100 parts of trimesic acid and 400 parts ofoctadecylamine is heated to from about 200 to 250 C. until about 20parts of water have distilled ofi. The residue forms after cooling 9.

pale brown hard wax-like mass having a dropping point of C.; it becomesplastic and flexible when heated.

What we claim is:

1. The process of producing a wax-like substance which comprisescondensing an aliphatic amine having at least one alkyl radical with atleast 8 carbon atoms and at least one hydrogen atom attached to nitrogenwith a cyclic dicarboxylic acid from which an anhydride can be formedonly by combination of two molecules 01 By using an equimolecular amountof octadec- 76 acid.

2. The process of producing a wax-like substance which comprisescondensiiig an aliphatic amine having at least one alkyl radical with atleast 8 carbon atoms and at least one hydrogen atom attached to nitrogenwith a cyclic dicarboxylic acid of the benzene series from which ananhydride can be formed only by combination of two molecules of acid.

3. The process of producing a wax-like substance which comprisescondensing an aliphatic amine derived from a fatty acid of vegetalorigin having at least 8 carbon atoms and at least one hydrogen atomattached to nitrogen with a cyclic dicarboxylic acid from which ananhydride can be formed only by combination of two molecules of acid.

4. The process of producing a wax-like substance which comprisescondensing an aliphatic amine with at least one alkyl radical containingat least 8 carbon atoms and at least one hydrogen atom attached tonitrogen with terephthalic acid.

5. The process of producing a wax-like substance which comprisescondensing an aliphatic amine with at least one alkyl radical containingat least 8 carbon atoms and at least onehydrogen atom attached tonitrogen with a cyclic dicarboxylic acid from which an anhydride can beformed only by combination or two molecules of acid and an aliphaticcarboxylic acid selected from the class consisting of aliphatic monoanddicarboxylic acids.

amide each CO is combined with the N of the radical of an aliphaticamine having at least one alkyl radical with at least 8 carbon atoms.

8. A diamide of a cyclic dicarboxylic acid of the benzene series, fromwhich an anhydride can be formed only by combination of two molecules ofacid, in which diamide each CO is combined with the N of the radical ofan aliphatic amine having at least one alkyl radical with at least 8carbon atoms.

9. A diamide of a cyclic dicarboxylic acid, from which an anhydride canbe formed only by com-v binatlon of two molecules of acid, in which di-6. The process of producing a wax-like sub stance which comprisescondensing a mixture of an aliphatic amine with at least one alkylradical containing at least 8 carbon atoms and an allphatic polyamineeach of the said amines containing at least one hydrogen atom attachedto nitrogen with a cyclic dicarboxylic acid from which an anhydride canbe formed only by combination of two molecules of acid.

7. A diamide of a cyclic dicarboxylic acid, from which an anhydride canbe formed only by combination of two molecules of acid, in which diamideeach CO is combined with the N of a the radical of an aliphatic aminederived from a fatty acid of vegetal origin having at least one alkylradical with at least 8 carbon atoms.

10. A diamide of terephthalic acid, in which diamide each CO is combinedwith the N of the radical of an aliphatic amine having at least onealkyl radical with at least 8 carbon atoms.

11. A wax-like condensation product from a cyclic dicarboxylic acid fromwhich an anhydride can be formed only by the combination of twomolecules of acid, an aliphatic carboxylic acid selected from the classconsisting of aliphatic monoand dicarboxylic acids, and an aliphaticamine having at least one alkyl radical containing at least 8 carbonatoms and at least one hydrogen atom attached to nitrogen.

12. A wax-like condensation product from a cyclic dicarboxylic acid fromwhich an anhydride can be formed only by the combination of twomolecules of acid, an aliphatic carboxylic acid selected from the classconsisting of aliphatic monoanddicarboxylic acids, and a mixtur of analiphatic amine having at least one alkyl radical containing at least 8carbon atoms and an aliphatic polyamine each of the said aminescontaining at least one hydrogen atom attached to nitrogen.

HANS GEORG HUMMEL. MICHAEL JAHRSTORFER.

